Direct in situ reduction of silver ions by a biopolymer such as agar, without any other reducing nor capping agent is shown in this article to lead either to nanoparticles (typically 12(2) nm in an optimized case) or to more complex nanostructures depending on the reaction conditions used. This approach takes advantage of the porous polymer lattice acting as a template and leads to hybrid Ag–Agar materials with long-term synergic stability. Silver acts as an antibacterial agent for agar whereas the biopolymer prevents agglomeration of the inorganic nanoparticles leading to a stable nanocomposite formed by a thermoreversible biopolymer from which silver nanoparticles can eventually be recovered.